Novel In-Situ Gelled Acid System Based on Inorganic Nanoparticles

Abstract

Gelled acid systems based upon gelation of hydrochloric acid (HCl) are widely used in in both matrix acidizing and fracture acidizing treatments to prevent acidizing fluid leak-off into high permeable zones of a reservoir. The gelled up fluid system helps retard the acid reaction to allow deeper acid penetration for hydrocarbon productivity enhancement. The in-situ gelation is typically achieved by using crosslinked polymers with the acid. Conventional in-situ crosslinked gelled acid systems are made up of polyacrylamide gelling agent, iron based crosslinker and a breaker chemical in addition to other additives, with the acid as the base fluid. However, the polymer-based systems can lead to damaging the formation due to a variety of reasons including unbroken polymer residue. Additionally, the iron-based crosslinker systems can lead to scaling, precipitation and or sludge formation after the acid reacts with the formation, resulting in formation damage and lowering of hydrocarbon productivity. In this paper we showcase a new nanoparticles based gelled acid system that overcomes the inherent challenges faced by conventional in-situ crosslinked gelled acid systems. The new system can work in 5 to 20 % HCl up to 300°F. The new system does not contain any polymer or iron based crosslinker that can potentially damage the formation. It comprises nanoparticles, a gelation activator, acidizing treatment additives along with HCl. The new in-situ gelled acid system has low viscosity at surface making it easy to pump. It gels up at elevated temperatures and pH of 1 to 4, which helps with diverting the tail end acid to tighter or damaged zones of the formation. We demonstrate that the viscosification and eventual gelation of the new system can be achieved as the acid reacts with a carbonate formation and the pH rises above 1. As the acid further reacts and continues to spend there by increasing the pH beyond 4, the gel demonstrates reduction of viscosity. This assists in a better cleanup post the acidizing treatment. Various experimental techniques were used to showcase the development of the nanoparticle based acid diversion fluid. Static and dynamic gelation studies as a function of time, temperature and pH are reported. The gelation performance of the new system was evaluated at temperatures up to 300°F and discussed in the paper. Comparative performance of different types of gelation activators on the gelation profile of the nanoparticles is evaluated. It is also shown that the gelation and viscosity reduction is entirely a pH dependent phenomenon and does not require any additional breaker chemistry, and therefore provides more control over the system performance. The novelty of the new gelled acid system is that it is based upon nanoparticles making it less prone to formation damage as compared to a crosslinked polymer based system.